CN101605829B - Polymers - Google Patents

Polymers Download PDF

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Publication number
CN101605829B
CN101605829B CN2007800512525A CN200780051252A CN101605829B CN 101605829 B CN101605829 B CN 101605829B CN 2007800512525 A CN2007800512525 A CN 2007800512525A CN 200780051252 A CN200780051252 A CN 200780051252A CN 101605829 B CN101605829 B CN 101605829B
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monomer
multipolymer
methyl
vinyl
chain
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CN101605829A (en
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保罗·休·芬德利
史蒂文·保罗·兰纳德
布罗迪克·詹姆斯·拉施兰·罗伊斯
乔纳森·维克托·马克·韦弗
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Unilever PLC
Unilever NV
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention relates to a branched polymer obtainable an addition polymerisation process, preferably a free-radical polymerisation process, which is the reaction product of: (a) an initiator, optionally but preferably a free-radical initiator, (b) optionally but preferably a compatible chain transfer agent (E and E'), (c) at least one ethyleneically monounsaturated monomer (G and/or J), (d) at least one ethyleneically polyunsaturated monomer (L), wherein at least one of (a)-(d) has a molecular weight of at least 1000 Daltons, and the mole ratio of (d) to (c) is greater than 0.0005 to 1.

Description

Polymkeric substance
The present invention relates to the for example purposes of deflocculant of branched polymer, their preparation method, the compsn that contains this multipolymer and their conducts.
Branched polymer is the polymer molecule that is designed to have finite size, is unlike under the obtainable condition of monomer growth and can becomes big cross-linked polymer arbitrarily.Opposite with cross-linked polymer, branched polymer is more solvable.Advantageously, compare with the solution of similar simple linear polymer, the soltion viscosity of branched polymer is lower.Big branched copolymers dissolves than corresponding simple linear polymer more easily.Branched polymer with many end groups can show stronger surface-treated performance.Branched polymer is the useful component that is used for many compsns in various fields.
Comb shape or graftomer are the structure subclass of branched polymer, have be connected on the main chain big, be generally the polymeric side group.
Branched polymer generally prepares via progressively increasing the polycondensation of mechanism through proper monomer, and it is limited the chemical functionality (chemical functionality) and the molecular weight of resulting polymkeric substance usually.Except polymerization, also can adopt single stage method, wherein polyfunctional monomer is used to provide the functionality that can grow the polymkeric substance side chain in the polymer chain.Yet the limitation in the use of conventional single stage method is: for fear of the formation of the crosslinked on a large scale and insoluble gel of polymkeric substance, usually must be carefully the amount of polyfunctional monomer be controlled to basically less than 0.5%w/w.Adopt this method to be difficult to avoid crosslinked, especially do not exist as the solvent of thinner and/or at monomer under the high conversion situation of polymkeric substance.
Grafting or comb(shaped)polymer are usually through preparing from the connection or the growth of the oligomeric or monomeric unit of preformed simple linear polymer respectively.As selection, grafting or comb(shaped)polymer can pass through oligomeric monomer, or " macromonomer " and conventional monomer or the more unitary mixture of minor comonomer addition polymerization and prepare.
Line-type block polymer is normally through the preparation of following method: after a kind of monomeric living polymerization was accomplished, the other and different usually monomers of follow-up adding were to obtain block structure.Living polymerization can also take place from the one or both ends of preformed polymkeric substance or oligopolymer, is called as the segmented copolymer of AB or ABA segmented copolymer respectively with preparation.
The outer segmented copolymer of branching (branched external block copolymer) can be counted as with respect to the core of branching more has outside or crown block structure.When preparing with the branching agent (brancher) of macromolecule or monomer, these polymkeric substance also have inner block and Grafting Structure respectively.
Block structure and Grafting Structure in the graft block copolymer of branching can be counted as and in the branched polymer structure, have.
WO 99/46301 discloses the method for preparing branched polymer; Said method comprising the steps of: the chain-transfer agent of the multifunctional vinyl monomer, 0.0001 to 50%w/w (in the weight of monofunctional monomer) of simple function vinyl monomer and 0.3 to 100%w/w (in the weight of monofunctional monomer) is admixed together with optional radical polymerization initiator; And, make said mixture reaction to form multipolymer afterwards.The embodiment of WO 99/46301 described be mainly hydrophobic polymer and especially wherein TEB 3K as the preparation of the polymkeric substance of monofunctional monomer.These polymkeric substance can be used as the component of top coat and ink or can be used as moulding resin.
WO 02/34793 discloses a kind of copolymer compositions that comprises multipolymer, and said multipolymer is by at least a unsaturated carboxylic acid monomer, at least a hydrophobic monomer, hydrophobic chain transfer agent, linking agent, and optional steric stabilizer produces.Said copolymer compositions plays the effect of rheology modifier, and reason is that it provides the viscosity of increase in containing electrolytical aqueous environments.
WO 02/16442 discloses through free radical polymerisation process, from the cross-linked hydrogel compsn of simple function and polyfunctional monomer preparation.Do not use chain-transfer agent, and in the radical dispersion polymerization, polymer complex is formed particulate.
Therefore the purpose of this invention is to provide a kind of polymkeric substance that more is prone to dissolve and does not increase during dissolving viscosity than crosslinked polymkeric substance.
Have now found that the branching non-cross-linked polymer can obtain through addition polymerization method, preferred radical polymerization, and said polymkeric substance can not increase viscosity in being dissolved in solvent the time, and they have various application owing to having favorable properties.
Therefore, first aspect of the present invention provides can be through addition (preferred radical) branched polymer that polymerization obtains, and said branched polymer is the reaction product of and the following:
(a) initiator, optional still preferred radical initiator,
(b) optional still preferred compatible chain-transfer agent (E and E '),
(c) the single unsaturated monomer of at least a ethylenic (ethyleneically) (G and/or J),
(d) the many unsaturated monomers of at least a ethylenic (L),
Wherein at least one in (a)-(d) has at least 1000 daltonian molecular weight, and (d) and mol ratio (c) greater than 0.0005: 1.
Amphipathic branched copolymers of the present invention is branching, noncrosslinking addition polymer, and comprises random, gradient (gradient) and branched copolymers alternately.Preferably, said branched polymer has general formula
Figure G2007800512525D00031
Wherein
E and E ' represent the residue of chain-transfer agent or initiator independently of one another;
G and J represent that independently of one another each molecule contains the residue of the monofunctional monomer of a polymerizable double bond;
L is the residue that each molecule contains the polyfunctional monomer of at least two polymerizable double bonds;
R and R ' represent Wasserstoffatoms or optional substituted alkyl independently of one another;
X and X ' represent to derive from the end group of termination reaction independently of one another;
G, j and l represent the mol ratio of each residue, and said mol ratio is made g+j=100 by normalization method,
Wherein
G and j represent 0 to 100 independently of one another; And l is >=0.05; And
M and n are independently of one another >=1; And
Among E, E ', G, J and the L at least one has at least 1000 daltonian molecular weight.
Second aspect of the present invention provides a kind of and prepares the method for this branched copolymers through addition polymerization method, preferred radical polymerization,
Said method comprises and the following is mixed together:
(a) at least a monofunctional monomer;
(b) polyfunctional monomer of at least 0.05 mole of % (based on the mole number of monofunctional monomer);
(c) optional still preferred chain-transfer agent; With
(d) initiator, optional still preferred radical initiator;
And, make said mixture reaction to form branched copolymers subsequently.
In the third aspect, the present invention provides a kind of compsn, particularly is laundry composition, and said compsn comprises the branched copolymers and the carrier of as above definition.
In fourth aspect, the present invention provides the purposes of the branched copolymers of as above definition as the component of laundry composition.
In aspect the 5th, the present invention provides the purposes of the branched copolymers of as above definition as deflocculant.
Definition
Relate to chemical structure, molecule segment and substituting group to give a definition:
As be meant the branching that can contain 1 to 12 carbon atom or the saturated hydrocarbyl of non-branching at this employed term " alkyl ", such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, octyl group, decyl etc.More preferably, alkyl contains 1 to 6, preferred 1 to 4 carbon atom.Methyl, ethyl and propyl group are preferred especially." substituted alkyl " is meant with the substituted alkyl of one or more substituting groups.Preferably, alkyl and substituted alkyl are non-branchings.
Typical substituting group comprises; For example: halogen atom, nitro, cyanic acid, hydroxyl, naphthenic base, alkyl, alkenyl, haloalkyl, alkoxyl group, halogenated alkoxy, amino, alkylamino, dialkyl amido, formyl radical, carbalkoxy, carboxyl, alkyloyl, alkyl sulfenyl (alkylthio), alkyl sulphinyl (alkylsulfinyl), alkyl sulphonyl, alkylsulphonic acid base (alkylsulfonato), aryl sulfonyl kia, aryl sulfonyl, aryl sulfonic acid groups (arylsulfonato), phosphinyl, phosphono, formamyl, amido, alkyl amido, aryl, aralkyl and quaternary ammonium group, like the beet base.In these substituting groups, halogen atom, cyanic acid, hydroxyl, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, amino, carboxyl, amido and quaternary ammonium group such as beet base are preferred especially.When alkyl or alkenyl substitutents are represented or contained to any above-mentioned substituting group, this substituting group can be a straight or branched, and can contain 12 at the most, preferably 6 and especially preferred 4 carbon atoms at the most at the most.Naphthenic base can contain 3 to 8, preferred 3 to 6 carbon atoms.Aromatic yl group or part can contain 6 to 10 carbon atoms, and phenyl is preferred especially.Halogen atom can be fluorine, chlorine, bromine or iodine atom, thereby and any group of Halogen part such as haloalkyl can contain any or multiple in these halogen atoms.
In the context of this specification sheets, term " cleaning " and/or " cleaning " expression " washing and/or rinsing ".
Term comprises methylacrylic acid and vinylformic acid like " (methyl) vinylformic acid ".Similarly term should be understood similarly.
Term comprises alkyl, alkaryl, aralkyl (for example phenmethyl) and aromatic yl group and part like " alkane/aryl (alk/aryl) ".
Molar percentage is based on total monofunctional monomer content.
Except the situation of other explanation, the molecular weight of monomer and polymkeric substance is expressed as weight-average molecular weight.
Multipolymer
Can be according to branched polymer of the present invention through the addition polymerization method, preferred radical polymerization obtains, and is the reaction product of and the following:
(a) initiator, optional still preferred radical initiator,
(b) optional still preferred compatible chain-transfer agent (E and E '),
(c) the single unsaturated monomer (G and/or J) of at least a ethylenic,
(d) the many unsaturated monomers of at least a ethylenic (L),
Wherein at least one in (a)-(d) has at least 1000 daltonian molecular weight, and (d) and mol ratio (c) greater than 0.0005: 1.
Branched polymer of the present invention is branching, noncrosslinking addition polymer, and comprises random, gradient and branched copolymers alternately.Preferably, branched polymer of the present invention has general formula
Figure G2007800512525D00051
Wherein
E and E ' represent the residue of chain-transfer agent or initiator independently of one another;
G and J represent that independently of one another each molecule contains the residue of the monofunctional monomer of a polymerizable double bond;
L is the residue that each molecule contains the polyfunctional monomer of at least two polymerizable double bonds;
R and R ' represent Wasserstoffatoms or optional substituted alkyl independently of one another;
X and X ' represent to derive from the end group of termination reaction independently of one another;
G, j and l represent the mol ratio of each residue, and said mol ratio is made g+j=100 by normalization method, and wherein g and j represent 0 to 100 independently of one another; And l is >=0.05; And m and n are independently of one another >=1; And
Among E, E ', G, J and the L at least one has at least 1000 daltonian molecular weight.
A kind of preferred polymers according to the present invention is comb shape or grafted branched polymer, and wherein at least one among G and the J has at least 1000 daltonian molecular weight, and L has the molecular weight below 1000 dalton.More preferably,, another among the G of said multipolymer and the J have the molecular weight below 1000 dalton if existing.Most preferably, molecular weight is hydrophilic monomers at least 1000 daltonian monofunctional monomers.Also more preferably, chain-transfer agent has the molecular weight below 1000 dalton.
Another kind of preferred polymers according to the present invention is the interior segmented copolymer of branching, and wherein G and J have the molecular weight below 1000 dalton, and L has at least 1000 daltonian molecular weight.More preferably, chain-transfer agent has the molecular weight below 1000 dalton.
Another kind of preferred polymers according to the present invention is the outer segmented copolymer of branching, and wherein chain-transfer agent has at least 1000 daltonian molecular weight, and G, J and L have the molecular weight below 1000 dalton.
The graft block copolymer that another kind of again preferred polymers according to the present invention is a branching, wherein G, J and L have at least 1000 daltonian molecular weight.More preferably, chain-transfer agent has at least 1000 daltonian molecular weight.
Multipolymer can also contain the unreacted vinyl from polyfunctional monomer.
Monofunctional monomer
Monofunctional monomer can comprise can pass through any carbon-to-carbon unsaturated compound of mechanism of addition polymerization polymeric, for example vinyl and allylic cpd.The character of monofunctional monomer can be wetting ability, hydrophobicity, amphipathic, negatively charged ion, positively charged ion, neutrality or zwitterionic.Monofunctional monomer can be selected from but be not limited to following monomer; Such as: the verivate of vinyl acids, vinyl acid esters, vinyl aromatic (co) based compound, vinyl acid anhydrides, vinylamide, vinyl ether, vinyl amine, ethenyl aromatic yl amine, vinyl nitrile, vinyl ketone and above-claimed cpd and the allyl group variant of their correspondence.Other suitable monofunctional monomer comprises: the monomer of hydroxyl with can afterreaction to form monomer, acidiferous or acid functional monomer, zwitterionic monomer and the quaternised amino monomers of hydroxyl.If having, G and/or J be higher than 1000 daltonian molecular weight; Then can also use oligomeric polymeric or few functionalized or multiple functionalized monomer; Particularly oligomeric or polymeric (methyl) esters of acrylic acid; Such as gathering (aklylene glycol) or gather list (alkane/aryl) (methyl) esters of acrylic acid of (dimethyl siloxane), or any other polymkeric substance or the mono-vinyl or allyl group adducts of oligopolymer.Can also use, gradient random to prepare or alternating copolymer more than a kind of monomeric mixture.Therefore, G and J represent the residue of aforesaid monofunctional monomer independently of one another.
Vinyl acids and verivate thereof comprise: (methyl) vinylformic acid and their acyl halide are like (methyl) acrylate chloride.Vinyl acid esters class and their verivate comprise: (methyl) vinylformic acid C1-20 alkyl ester (straight chain and side chain) is like (methyl) methyl acrylate, (methyl) vinylformic acid stearyl and (methyl) 2-EHA; (methyl) aryl acrylate; Like (methyl) benzyl acrylate; (methyl) vinylformic acid three (alkoxyl group) silyl alkyl ester is like (methyl) vinylformic acid trimethoxysilyl propyl ester, and (methyl) acrylic acid active ester such as amino (methyl) propenoate of N-hydroxyl succinyl-.Vinyl aromatic (co) based compound and verivate thereof comprise: vinylbenzene, acetoxy-styrene, styrene sulfonic acid, vinyl pyridine, vinyl benzyl chloride and vinyl benzoic acid.Vinyl acid anhydrides and verivate thereof comprise maleic anhydride.Vinylamide and verivate thereof comprise: (methyl) acrylic amide, N-vinyl pyrrolidone, N-vinyl formamide, (methyl) acrylamido oxypropyl trimethyl ammonium chloride, [3-((methyl) acrylamido) propyl group] trimethyl ammonium chloride, 3-[N-(3-(methyl) acrylamido propyl group)-N, N-dimethyl-] aminopropanesulfonic acid ester, methyl (methyl) acrylic amide ethyl glycolate methyl ether and N-sec.-propyl (methyl) acrylic amide.Vinyl ether and verivate thereof comprise methylvinylether.Vinyl amine and verivate thereof comprise: (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid diisopropylaminoethyl ethyl ester, (methyl) vinylformic acid list tertiary butyl amino ethyl ester, (methyl) vinylformic acid morpholino ethyl ester with can afterreaction to form amino monomer, such as vinyl formamide.Ethenyl aromatic yl amine and verivate thereof comprise: vinyl aniline, vinyl pyridine, N-VCz and vinyl imidazole.Vinyl nitrile and verivate thereof comprise (methyl) vinyl cyanide.Vinyl ketone and verivate thereof comprise acreolin.
The monomer of hydroxyl comprises: the vinyl hydroxy monomer is like single (methyl) propenoate of (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, glycerine list (methyl) propenoate and sugar such as glucose list (methyl) propenoate.Can comprise with the monomer that forms hydroxyl by afterreaction: vinyl-acetic ester, acetoxy-styrene and (methyl) glycidyl acrylate.Acidiferous or acid functional monomer comprises: (methyl) vinylformic acid, styrene sulfonic acid, vinyl phosphonate, vinyl benzoic acid, toxilic acid, fumaric acid, methylene-succinic acid, 2-(methyl) acrylamido 2-ethyl propanesulfonic acid, mono succinate-2-((methyl) acryloxy) ethyl ester and ammonium sulfate close (methyl) ethyl propenoate (ammonium sulfatoethyl (meth) acrylate).Zwitterionic monomer comprises: (methyl) acryloxy ethyl Phosphorylcholine and the monomer that contains trimethyl-glycine, and such as [2-((methyl) acryloxy) ethyl] dimethyl--(3-sulfo group propyl group) volatile caustic.Quaternised amino monomers comprises: (methyl) acryloxy ethyl three (alkane/aryl) ammonium halide, and such as (methyl) acryloxy ethyl-trimethyl salmiac.
Polymerization single polymerization monomer comprises: gather (methyl) esters of acrylic acid, such as list (alkane/aryl) oxygen base polyalkylene oxide (methyl) propenoate and single (alkane/aryl) oxygen base YSR 3286 (methyl) propenoate.These esters comprise: mono methoxy polyethylene glycol list (methyl) propenoate, mono methoxy W 166 list (methyl) propenoate, monohydroxy polyethyleneglycol (methyl) propenoate and monohydroxy W 166 list (methyl) propenoate.Other instance comprises through the formed preparatory formation of ring-opening polymerization (being total to) polymkeric substance as gathering (hexanolactam) or gathering vinyl or allyl ester, acid amides or the ether of (caprolactone); Or through the formed polymkeric substance of living polymerization technology as gathering (1, the 4-divinyl).Under suitable situation, can also use corresponding oligopolymer.
The allyl monomer of listed monomeric correspondence more than can also using under the suitable situation.
Preferred monomer comprises:
The monomer of amide containing is like (methyl) acrylic amide, N; N '-dimethyl-(methyl) acrylic amide, N and/or N '-two (alkyl or aryl) (methyl) acrylic amide, N-vinyl pyrrolidone, [3-((methyl) acrylamido) propyl group] trimethyl ammonium chloride, 3-(dimethylamino) propyl group (methyl) acrylic amide, 3-[N-(3-(methyl) acrylamido propyl group)-N; The N-dimethyl-] and aminopropanesulfonic acid ester, methyl (methyl) acrylamido ethyl glycolate methyl ether and N-sec.-propyl (, methyl) and acrylic amide;
(methyl) vinylformic acid and verivate thereof be like (methyl) vinylformic acid, (methyl) acrylate chloride (or any halogen), (methyl) vinylformic acid (alkyl) ester, and functionalized polymerization single polymerization monomer such as mono methoxy gathers (terepthaloyl moietie) single (methyl) propenoate, mono methoxy and gather that (Ucar 35) single (methyl) propenoate, monohydroxy gather (terepthaloyl moietie) single (methyl) propenoate, monohydroxy gathers (Ucar 35) single (methyl) propenoate, glycerine list (methyl) propenoate and single (methyl) propenoate of sugar such as glucose list (methyl) propenoate;
The vinyl amine as (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) vinylformic acid diisopropylaminoethyl ethyl ester, (methyl) vinylformic acid list tertiary butyl amino ethyl ester, (methyl) vinylformic acid morpholino ethyl ester, ethenyl aromatic yl amine such as vinyl aniline, vinyl pyridine, N-VCz, vinyl imidazole and can afterreaction to form the monomer such as the vinyl formamide of amido;
The ethenyl aromatic yl monomer is like vinylbenzene, vinyl chloride, Vinyl toluene, alpha-methyl styrene, styrene sulfonic acid and vinyl benzoic acid;
The vinyl hydroxy monomer, like (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, glycerine (methyl) propenoate, or monomer such as vinyl-acetic ester, acetoxy-styrene and (methyl) glycidyl acrylate that can functionalized later on one-tenth hydroxyl;
Acidiferous monomer is like (methyl) vinylformic acid, styrene sulfonic acid, vinyl phosphonate, vinyl benzoic acid, toxilic acid, fumaric acid, methylene-succinic acid, 2-(methyl) acrylamido 2-ethyl propanesulfonic acid and mono succinate-2-((methyl) acryloxy) ethyl ester or acid anhydrides such as maleic anhydride;
Zwitterionic monomer is like (methyl) acryl oxygen base ethyl PC and betaines, such as [2-((methyl) acryloxy) ethyl] dimethyl--(3-sulfo group propyl group) volatile caustic;
Quaternised amino monomers is like (methyl) acryloxy ethyl-trimethyl salmiac.
Under applicable situation, can also use corresponding allyl monomer in all cases.
Macromonomer (molecular weight is at least 1000 daltonian monomers) is normally through being connected to preformed monofunctional polymer on formed via suitable connector element such as ester, acid amides or ether polymerisable part such as vinyl or allyl group.The instance of suitable polymers comprises: simple function gathers (oxirane) like mono methoxy [gathering (terepthaloyl moietie)] or mono methoxy [gathering (Ucar 35)]; Siloxanes is as gathering (dimethyl siloxane) class; The polymkeric substance that forms through ring-opening polymerization is as gathering (caprolactone) or gathering (hexanolactam); Or through the formed monofunctional polymer of living polymerization, as gather (1, the 4-divinyl).
Preferred macromonomer comprises: mono methoxy [gathering (terepthaloyl moietie)] single (methacrylic ester), mono methoxy [gathering (Ucar 35)] single (methacrylic ester) and single (methyl) acryloxy propyl group-end capped gathering (dimethyl siloxane).
Can also use the functional monomer; Promptly having can be at the monomer of the reactivity side group of modifying or modifying in advance after with another part after the polyreaction, such as (methyl) glycidyl acrylate, (methyl) vinylformic acid three (alkoxyl group) silyl alkyl ester, (methyl) acrylate chloride, maleic anhydride, (methyl) acrylic acid hydroxy alkyl ester, (methyl) vinylformic acid, vinyl chloride, (methyl) acrylic acid active ester like (methyl) vinylformic acid N-hydroxyl succinyl-amino ester and acetoxy-styrene.
Polyfunctional monomer
Polyfunctional monomer or branching agent (brancher) can comprise that containing at least two can pass through polyaddition reaction and the molecule of polymeric vinyl.Said molecule can be wetting ability, hydrophobicity, amphipathic, neutral, positively charged ion, zwitter-ion or oligomeric.This molecule is commonly called linking agent in this area, and can prepare through making any two senses or multifunctional molecule and suitable reactive monomer reaction.Polyfunctional monomer must have the molecular weight below 1,000 dalton.Instance comprises: divinyl or many vinyl ester, divinyl or many vinylamides, divinyl or many vinyl aromatic (co)s based compound and divinyl or many vinyl alkane/aryl ethers.Typically, under the situation of oligomeric or multifunctional branching agent, ligation is used to be connected on two senses or the multifunctional oligopolymer polymerizable moiety or on two senses or the multifunctional group.Branching agent itself can have the branch point more than, such as T shape divinyl oligopolymer.In some cases, can use more than a kind of polyfunctional monomer.
The allyl monomer of the correspondence of listed compound more than can also using under the suitable situation.
Preferred polyfunctional monomer includes but not limited to: divinyl aryl monomer such as Vinylstyrene class; (methyl) diester acrylates class is such as ethylene glycol bisthioglycolate (methyl) propenoate, Ucar 35 two (methyl) propenoate and 1,3 butylene glycol two (methyl) propenoate; Low polyalkylene oxide two (methyl) esters of acrylic acid is such as TEG two (methyl) propenoate, oligomeric (terepthaloyl moietie) two (methyl) propenoate and oligomeric (Ucar 35) two (methyl) propenoate; The divinyl acrylic amide is such as methylene-bisacrylamide; The divinyl ester class or the amides that contain siloxanes are such as (methyl) acryloxy propyl group end capped oligomeric (dimethyl siloxane); The divinyl ethers is such as oligomeric (terepthaloyl moietie) divinyl ether; With four-and or three-(methyl) esters of acrylic acids, such as tetramethylolmethane four (methyl) propenoate, trimethylolpropane tris (methyl) propenoate or glucose two-to five (methyl) propenoate.Other instance comprises vinyl or allyl ester, acid amides or the ether of following oligopolymer: through the formed preformed oligopolymer of ring-opening polymerization such as oligomeric (hexanolactam) or oligomeric (caprolactone); Or through the living polymerization formed oligopolymer of technology such as oligomeric (1, the 4-divinyl).
Macromolecules cross-linking agent agent or macromole branching agent (molecular weight is at least 1000 daltonian polyfunctional monomers) normally form on the preformed polyfunctional poly compound through polymerisable part such as vinyl or aryl are connected to via suitable connector element such as ester, acid amides or ether.The instance of suitable polymers comprises: two senses gather (oxirane) as gather (terepthaloyl moietie) or gather (Ucar 35), type siloxane as gather (dimethyl siloxane) type, through the formed polymkeric substance of ring-opening polymerization as gathering (caprolactone) or gathering (hexanolactam); Or through the formed polyfunctional poly compound of living polymerization as gathering (1, the 4-divinyl).
Preferred macromole branching agent comprises: gather (terepthaloyl moietie) two (methyl) propenoate, gather (Ucar 35) two (methyl) propenoate, (methyl) acryloxy propyl group-end capped gathering (dimethyl siloxane), gather (caprolactone) two (methyl) propenoate and gather (hexanolactam) two (methyl) acrylic amide.
Therefore, L is the residue of aforesaid polyfunctional monomer.
Multipolymer must contain polyfunctional monomer.In other words, in formula (I), 1 be >=0.05.It is preferably 0.05 to 50, and more preferably 0.05 to 40, especially be 0.05 to 30 and be in particular 0.05 to 15.
Chain-transfer agent
Chain-transfer agent is the known molecule that in the process of Raolical polymerizable, reduces molecular weight through chain transfer mechanism.These reagent can be any molecules that contains mercaptan, and can be simple functions or polyfunctional.Said reagent can be wetting ability, hydrophobicity, amphipathic, negatively charged ion, positively charged ion, neutrality or zwitterionic.Said molecule can also be the oligopolymer that contains thiol moiety.(said reagent can also be hindered alcohols or similar free radical stabilizer).Can also use catalytic chain transfer agent, such as based on transition metal complex such as two (boron difluoro dimethyl--glyoxime) cobalt ((CoBF) those of cobaltbis (borondifluorodimethyl-glyoximate).Suitable mercaptan includes but not limited to: C2-C18 alkyl sulfhydryl such as dodecyl mercaptans, thioglycolic acid, thioglycerin, halfcystine and thioethanolamine.Can also use the oligopolymer or polymkeric substance such as the oligomeric halfcystine that contain mercaptan, or functionalized by the back so that the oligopolymer of one or more thiol groups to be provided, such as low polyoxyethylene glycol acyl (two) thioglycolic acid ester.Can also use xanthate class, dithioesters class and dithiocarbonates class, such as the withered ester of phenyl methyl-carbithionic acid.Alternative chain-transfer agent can be any species of the molecular weight of known limitation in the radical addition polymerization reaction, comprises alkylogen and transition metal salt or complex compound.Can make up use more than a kind of chain-transfer agent.
The residue of chain-transfer agent can account for 0 to 50 mole of % of multipolymer, preferred 0 to 40 mole of % and be in particular 0.05 to 30 mole of % (based on the mole number of monofunctional monomer).
Initiator is radical initiator and can is any molecule of known initiation Raolical polymerizable, such as the molecule that contains azo, persulphate, redox initiator, superoxide, benzyl ketone.They can be activated through heat, photodissociation or chemical means.Their instance includes but not limited to: 2, and 2 '-Diisopropyl azodicarboxylate (AIBN), azo two (4-cyanovaleric acid), Lucidol, peroxo-cumyl, 1-hydroxycyclohexylphenylketone, hydrogen peroxide/xitix.Can also use iniferter such as N, N-diethyldithiocar bamic acid benzyl ester.In some cases, can use more than a kind of initiator.
Preferably, based on monomeric gross weight, in the Raolical polymerizable residue of initiator account for multipolymer 0 to 5%w/w, preferred 0.01 to 5%w/w and be in particular 0.01 to 3%w/w.
The use of chain-transfer agent and initiator is preferred.Yet some molecules can play two kinds of effects.Preferably, the residue of an expression chain-transfer agent among E and the E ', and the residue of another expression initiator among E and the E '.
R in the preferred formula (I) and R ' represent Wasserstoffatoms or C1-4 alkyl independently of one another.
X and X ' represent to derive from the end group of termination reaction independently of one another.In the process of conventional radical polymerization reaction, some intrinsic and inevitable termination reactions take place.Termination reaction between the common radical typically is that bimolecular combines and disproportionation reaction, and they change and cause the elimination of two radicals according to monomer structure.It is the most general that disproportionation reaction is considered to, and especially for the polyreaction of (methyl) esters of acrylic acid, and relates to two dead elementary chains, one have the hydrogen end (X or X '=H), and another have carbon-to-carbon double bond (X or X '=-C=CH 2).When termination reaction was chain transfer reaction, X or X ' typically were the atoms that can easily capture, are generally hydrogen.Therefore, for example, when chain-transfer agent was mercaptan, X and/or X ' can be Wasserstoffatomss.
As becoming significantly from formula (I), m+I equals the number of polymerisable group in L, and n is the sum of repeating unit of copolymer.Preferably, m is 1 to 6, more preferably 1 to 4.
Synthesizing of multipolymer
Multipolymer is through the preparation of addition polymerization method, and said addition polymerization method is to use the conventional radical polymerization technology of chain-transfer agent.In order to be equipped with branched polymer, in the presence of chain-transfer agent and radical initiator, make monofunctional monomer and polyfunctional monomer or branching agent polymerization through the conventional radical polymerization legal system.Polyreaction can be carried out through solution, body, suspension, dispersion and emulsion process.
Therefore, the present invention also provides the method through addition (preferred radical) polymerization as above defined comb shape of preparation or grafting branched copolymers, and said addition polymerization method comprises following compound is mixed together:
(a) at least a as before defined monofunctional monomer;
(b) at least 0.05 mole of %'s (based on the mole number of monofunctional monomer) like preceding defined polyfunctional monomer;
(c) optional but preferred as before defined chain-transfer agent; With
(d) initiator, optional but preferred as before defined radical initiator;
And make said mixture reaction subsequently to form branching, noncrosslinking multipolymer.
Compsn
Multipolymer according to the present invention can be incorporated in the compsn, and said compsn only contains carrier or thinner (they can comprise solid and/or liquid) or also comprises activeconstituents.Said compound typically with 0.01% to 50%, particularly 0.01% to 25 weight %, preferred 0.05% to 15%, more preferably 0.1% to 10%, especially 0.1% to 5% and most preferably 0.2% to 1.5% content be comprised in the said compsn.
For particular molecular weight, when with the similar polymer phase of line style than the time, multipolymer of the present invention can show following character, such as viscosity reduce, deposition increases, particle/molecular dispersion increases, lubricated increase and solubleness increases.The structure of polymkeric substance can also influence the pKa of polyprotonic acid or alkali.Therefore, multipolymer of the present invention can use in various application.Yet multipolymer of the present invention is particularly suitable in laundry composition, using, particularly using as deflocculant.
Synthetic copolymer uses as deflocculant in laundry product usually.Part polymer scale is incorporated on the colloidal particles (dust dummy (dirt mimic)), simultaneously another part with particle stabilized in solution and prevent to deposit again.Have been found that branched polymer of the present invention increases the efficient of colloid-stabilisedization through steric hindrance mechanism.
Activeconstituents in the compsn is preferably tensio-active agent or fabric regulator.Can comprise more than a kind of activeconstituents.Can use the mixture of activeconstituents for some application.
Compsn of the present invention can be in any physical form, for example, and solid such as powder or particle, tablet, solid stylus, paste, gel or liquid, particularly water fluid.Particularly, said compsn can be used in the laundry composition, in liquid, powder or tablet laundry composition.
Compsn of the present invention is preferably laundry composition, particularly main (fabric washing) compsn or the rinsing interpolation softening compositions washed.If suitable, main cleaning composition can comprise fabric softening agent, and the rinse-added fabric softening compositions can comprise surface active cpd, especially the non-ionic surfactant compound.
Organic detersive surfactant
Detergent composition of the present invention can contain the surface active cpd (tensio-active agent) that can be selected from and the following: the anionic of soap and non-soap, cationic, non-ionic type, both sexes and amphoteric ionic surfactant compound and their mixture.Many suitable surface active cpds are available and are described in fully in the document, for example by Schwartz, Perry and Berch at " tensio-active agent and washing composition (Surface-Active Agents and Detergents) ", among volume I and the II.
Preferred operable decontamination active compound is the anionic and the nonionic compound of soap and the non-soap of synthetic.The total amount of the tensio-active agent that exists is aptly in the scope of 5 to 60 weight %, preferred 5 to 40 weight %.
Compsn of the present invention can contain aniorfic surfactant.Instance comprises: sulfonated alkylbenzene is the linear alkylbenzene sulfonate of C8-C15 such as linear alkylbenzene sulfonate, particularly alkyl chain length.The content of preferred linear alkylbenzene sulfonate is 0 weight % to 30 weight %, more preferably 1 weight % to 25 weight %, 2 weight % to 15 weight % most preferably.
Combination of the present invention can contain other aniorfic surfactant with the amount that is appended to the above-mentioned per-cent of quoting.Suitable AS is well-known for those skilled in the art.Instance comprises: primary alkyl sulphates and secondary alkyl sulfate, particularly C8-C20 primary alkyl sulphates; Sulfated alkyl ether; Alkene sulfonate; Alkylxylene sulfonate; The dialkyl sulfosuccinate succinate; And fatty sulfonate.Common particular certain cancers.
Compsn of the present invention can also contain non-ionics.Operable non-ionics comprises: primary alcohol ethoxylate and secondary alcohol ethoxyl compound; Every mole the alcohol C8-C20 fatty alcohol that carries out ethoxylation with average 1 to 20 mole oxyethane particularly, and every mole the alcohol C10-C15 uncle's fatty alcohol and the secondary fatty alcohol that carry out ethoxylation with average 1 to 10 mole oxyethane more particularly.The non-ionics of non-ethoxylatedization comprises: alkyl poly glucoside, glycerol monoethers and polyhydroxyamide (Portugal's acid amides (glucamide)).
The content of preferred non-ionics is 0 weight % to 30 weight %, preferred 1 weight % to 25 weight %, 2 weight % to 15 weight % most preferably.
Also feasible is to comprise to be used for fabric some monoalkyl cationic type tensio-active agent with main cleaning composition.Operable cationic surfactant comprises general formula R 1R 2R 3R 4N +X -Quaternary ammonium salt, wherein the R group is long or short hydrocarbon chain, typically is the alkyl of alkyl, hydroxyalkyl or ethoxylation, and X is counter ion (for example, R wherein 1Be the C8-C22 alkyl, preferred C8-C10 or C 12-C14 alkyl, R 2Be methyl, and R that can be identical or different 3And R 4Compound for methyl or hydroxyethyl); And cationic ester (for example, cholinesterase).
Operable both sexes and amphoteric ionic surfactant comprise: alkyl amine oxide, betaines and sultaine class.According to the present invention, detersive surfactant (a) most preferably comprises randomly and one or more cosurfactant blended anionic sulphonate or sulfosalt surfactants of being selected from the and the following: sulfate anion type tensio-active agent, cationic surfactant, amine oxide, alkanolamide and their combination of the non-ionics of ethoxylation, the non-ionics of non-ethoxylatedization, ethoxylation.
The selection of surface active cpd (tensio-active agent) and the amount of existence depend on the desired use of detergent composition.In fabric cleaning composition, know like skilled formulator, can be the hand washing product and the product that is intended to be used for different types of washing machine is selected the different surface active agents system.
The total amount of the tensio-active agent that exists also depends on the end-use of expection and for example can be up to 60 weight % at the compsn that is used for hand-washing fabric.At the compsn of the machine washing that is used for fabric, the amount of 5 to 40 weight % is normally suitable.Typically, compsn comprises the tensio-active agent of at least 2 weight %, for example 2-60%, preferred 15-40%, 25-35% most preferably.
Be applicable to that most of detergent composition of fabric washing machine automatically comprises the non-soap surfactant of anionic or non-ionics or this two combination with any proper ratio usually, randomly together with comprising soap.
Any fabrics in general regulator may be used in the compsn of the present invention.Regulator can be cationic or non-ionic type.Be used in main washing in the detergent composition if fabric is regulated compound, then this compound typically is non-ionic type.In order in rinse stage, to use, they typically are cationic.For example, they can with composition weight 0.5% to 35%, preferred 1% to 30%, more preferably 3% to 25% amount uses.
Preferably, one or more fabric regulators have chain alkyl or the alkenyl chain of two mean chain lengths separately more than or equal to C16.Most preferably at least 50% chain alkyl or alkenyl have the above chain length of C18.Preferably the chain alkyl of fabric regulator or alkenyl mainly are straight chains.
Fabric regulator is preferably provides excellent remollescent compound, and it is characterized in that chain fusion L β to L α transition temperature be higher than 250C, preferably be higher than 350C, most preferably be higher than 450C.This L β to L α changes can pass through dsc measurement, as " lipid bilayer handbook (Handbook of LipidBilayers), D Marsh, CRC Press, Boca Raton, Florida, 1990 (the 137th and 337 pages) are middle to be specified.
Undissolved basically fabric in the context of the present invention is regulated compound to be defined as 20 ℃ of solubleness in softening water less than 1 * 10 -3The fabric of weight % is regulated compound.Preferably, fabric softening compound has less than 1 * 10 -4Weight %, most preferably less than 1 * 10 -8To 1 * 10 -6Solubleness.Preferred cation type fabric softener comprises water miscible basically quaternary ammonium material; Said quaternary ammonium material comprises single alkyl or the alkenyl long-chain of mean chain length more than or equal to C20, or more preferably comprises terminal polar group and two mean chain lengths more than or equal to the alkyl of C14 or the compound of alkenyl chain.
Preferably, cationic fabric softener is quaternary material or the quaternary material that contains at least one ester group.The quaternary ammonium compound that contains at least one ester group is called as the quaternary ammonium compound that ester connects in this article.
As employed in the context of quaternary ammonium cation type fabric softener, term " ester group " comprises the ester group as linking group in the molecule.
The quaternary ammonium compound that ester connects preferably comprises plural ester group.The situation that all preferred one or more ester groups are the linking group between nitrogen-atoms and the alkyl in monoesters and diester quat.One or more ester groups preferably are connected on the nitrogen-atoms through another alkyl.
The quaternary ammonium compound that further preferably contains at least one ester group, preferred two ester groups; Wherein the group of at least one higher molecular weight contains at least one ester group; And the group of two or three lower molecular weights is connected on the shared nitrogen-atoms to produce positively charged ion; And wherein the charge balance negatively charged ion is halogen, acetate moiety or rudimentary alcoxyl sulfate radical (lower alkosulphate) ion, such as chlorine or methoxy sulfate radical (methosulphate).The substituting group of the higher molecular weight on the nitrogen is preferably and contains 12 to 28, preferred 12 to 22; The senior alkyl of 12 to 20 carbon atoms for example; Such as cocounut oil alkyl (coco-alkyl), tallow alkyl, hydrogenated tallow alkyl or substituted senior alkyl; And the lower molecular weight substituting group is preferably the low alkyl group of 1 to 4 carbon atom, such as methyl or ethyl, or substituted low alkyl group.One or more in the said lower molecular weight substituting group can comprise aryl moiety or can be replaced by aryl such as benzyl, phenyl or other suitable substituents.
Preferably; The quaternary ammonium material is connected to C12-C22 alkyl or the compound of alkenyl on the quaternary ammonium end group for having two through at least one ester bond (ester link), preferred two ester bonds, or comprises the compound that mean chain length is equal to or greater than the single long-chain of C20.
More preferably, the quaternary ammonium material comprises that having two mean chain lengths is equal to or greater than the chain alkyl of C14 or the compound of alkenyl chain.Also more preferably each chain all has the mean chain length that is equal to or greater than C16.Most preferably, at least 50% of each chain alkyl or alkenyl has the chain length of C18.Preferred chain alkyl or alkenyl are mainly the situation of straight chain.
The ester of the most preferred type that can in rinsing clothes compsn according to the present invention, use connects the quaternary ammonium material and is represented by formula (A):
Figure G2007800512525D00171
Wherein T does Or
Figure G2007800512525D00173
Each R 20Group is independently selected from: C 1-4Alkyl, hydroxyalkyl or C 2-4Alkenyl; And each R wherein 21Group is independently selected from: C 8-28Alkyl or alkenyl; Y -Be any suitable counter ion, i.e. halogen, acetate moiety or rudimentary alcoxyl sulfate ion are such as chlorine or methoxy sulfate radical; W is the integer of 1-5 or is 0; And y is the integer of 1-5.Preferred especially each R 20Group is that methyl and w are 1 or 2.
From environment reason advantageously the quaternary ammonium material be biodegradable situation.
Preferred this type material such as chlorination 1,2 two [sclerosis tallow acyloxy]-3-TMA(TriMethylAmine) propane and preparation method thereof for example is described among the US-A-4137180.As described in US-A-4137180, preferably, these materials comprise the monoesters of a spot of correspondence, for example chlorination 1-sclerosis tallow acyloxy-2-hydroxyl-3-TMA(TriMethylAmine) propane.
Being used for connecting the quaternary ammonium material at the another kind of preferred ester that rinsing clothes compsn according to the present invention uses can be expressed from the next:
Figure G2007800512525D00181
Wherein T does
Figure G2007800512525D00182
And R wherein 20, R 21, w and Y -As above-mentioned defined.
In the compound of formula (B), can be available from two of Hoechst-(tallow acyloxy ethyl)-alkyl dimethyl ammonium chloride is most preferred.From two of Hoechst-(sclerosis tallow acyloxy ethyl) alkyl dimethyl ammonium chloride and methoxy sulfuric acid two-(tallow acyloxy ethyl)-dimethyl hydroxyethyl ester also is preferred.
Another kind of preferred quaternary ammonium cation type fabric softener is defined by formula (C) :-
Figure G2007800512525D00183
R wherein 20, R 21And Y -As defined in the preceding text.
The material of preferred formula (C) is two-sclerosis tallow diethylammonium ammonium chloride of selling with trade mark Arquad 2HT.
As be known in the art, randomly the quaternary ammonium material of ester connection can contain other optional component, especially; Low molecular weight solvent; For example Virahol and/or ethanol and altogether promoting agent (co-active) like the non-ionic type tenderizer, for example lipid acid or sorbitan ester.
Decontamination lotion promoter
Main when washing fabric cleaning composition when being used as, compsn of the present invention also contains one or more decontamination lotion promoters usually.The total amount of decontamination lotion promoter is typically in the scope of 0 to 80 weight %, preferred 0 to 60 weight % in the compsn.
The inorganic builders that can exist comprises: yellow soda ash combines with the crystal seed that is used for lime carbonate, as disclosed among the GB 1437950 (Uniliver) in case of necessity; Crystallization and amorphous aluminosilicate, for example, like disclosed zeolite in GB 1473201 (Henkel), like disclosed amorphous aluminosilicate in GB 1473202 (Henkel) with like disclosed blended crystallization/amorphous aluminosilicate in GB 1470250 (P&G); And like disclosed layered silicate in EP 164514B (Hoechst).Inorganic phosphate builders, for example sodium orthophosphate, trisodium phosphate and tripoly phosphate sodium STPP also are suitable for using with the present invention.
Compsn of the present invention preferably contains the alkali metal aluminosilicate washing assistant, preferred sodium aluminium silicate washing assistant.The sodium aluminium silicate class can combine with the amount of 5 to 60 weight % (anhydrous benchmark), preferred 10 to 50 weight %, particularly 25 to 50 weight % usually.
Alkali metal aluminosilicate can be crystalline or amorphous or their mixture, general formula is: 0.8-1.5Na 2O.Al 2O 3.0.8-6SiO 2
These materials contain some combination water and must have the calcium ion-exchanged capacity that is at least 50mg CaO/g.Preferred sodium aluminium silicate class contains 1.5-3.5SiO 2Unit (in above-mentioned formula).Like what in document, prove absolutely, amorphous and crystalline material all can the preparations easily through the reaction between water glass and the sodium aluminate.Suitable crystalline aluminium water glass IX decontamination lotion promoter for example is described among the GB 1429143 (P&G).Preferred this type of sodium aluminium silicate is well-known commercially available zeolite A and X, and their mixture.
Zeolite can be to be widely used for clothing at present with the commercially available zeolite 4A in the washing powder.In an alternative embodiment of the present invention, be attached in the present composition zeolite builders for as described in EP384070A (Uniliver) and require the high alumina zeolite P (maximumaluminium zeolite P) (zeolite MAP) of protection.Zeolite MAP is defined as the alkali metal aluminosilicate of zeolite P type, and the ratio of its silicon and aluminium is no more than 1.33, preferably in 0.90 to 1.33 scope, more preferably in 0.90 to 1.20 scope.
Under the situation of zeolite MAP, the ratio of preferred especially silicon and aluminium is no more than 1.07, more preferably from about 1.00 zeolite MAP.The calcium binding capacity of zeolite MAP is generally in the anhydrous substances of every g 150mg CaO at least.
Zeolite can for example amorphous aluminosilicate or layered silicate be augmented like the SKS-6 from Clariant by other inorganic builders.
Zeolite can be augmented by organic washing-assisting detergent.The organic washing-assisting detergent that can exist comprises: polycarboxylate polymer, such as polyacrylate, vinylformic acid/maleic acid and vinylformic acid phosphinate; The monomeric polycarboxylates class is such as citric acid salt, glyconic acid salt, oxidation disuccinate class, glycerine monosuccinic acid ester, glycerine disuccinic acid ester and glycerine three succinates, succsinic acid carboxylic methoxyethoxy ester, propanedioic acid carboxylic methoxyethoxy ester class, picolinic acid hydrogen salt (dipicolinate), oxalic acid hydroxyethyl imines ester, propanedioic acid alkyl ester, propanedioic acid alkenyl ester, succsinic acid alkyl ester and succsinic acid alkenyl ester; And alpha-sulfonated fatty hydrochlorate.This enumerates and does not mean is exhaustive.
Preferred especially organic washing-assisting detergent is a citric acid salt, aptly with 1 to 30 weight %, preferred 5 to 30 weight %, the more preferably amount use of 10 to 25 weight %; With, XPA is more particularly vinylformic acid/maleic acid, uses with the amount of 0.5 to 15 weight %, preferred 1 to 10 weight % aptly.
Inorganic and organic washing-assisting detergent all preferably exists with the form of an alkali metal salt, particularly sodium salt.
Washing assistant aptly with total amount be 10 to 80 weight %, more preferably 20 to 60 weight % exist.Washing assistant can be inorganic or organic.
The decontamination lotion promoter that is selected from and the following (b) that can most preferably comprise 10 to 80 weight % according to lotion-aid combination of the present invention: zeolite, phosphoric acid salt and Citrate trianion.
Other stain remover component
Laundry detergent compositions comprises other detergent component of knowing in this area usually.These components can be selected from aptly: bleach, enzyme, yellow soda ash, water glass, sodium sulfate, Foam Control, profoamer, spices, fabric regulator, soil release polymer, dye transfer inhibitor, photobleaching agent, white dyes and colored particle (coloured speckle).
Can also contain bleach system aptly according to compsn of the present invention.Fabric cleaning composition can contain the peroxy bleaching compound that can in the aqueous solution, obtain hydrogen peroxide, for example inorganic persalt or organic peroxide acid (peroxyacids) aptly.
Suitable peroxy bleaching compound comprises: organo-peroxide such as urea peroxide and inorganic persalt such as alkali metal perborate, percarbonate, perphosphate, persilicate and persulphate.Preferred inorganic persalt is sodium perborate monohydrate and four hydrated sodium perborates, and SPC-D.
Particularly preferably be and have the SPC-D of resisting the caused unsettled supercoat of moisture.SPC-D with the supercoat that comprises sodium metaborate and water glass is disclosed among the GB 2123044B (flower king).
Peroxy bleaching compound exists with the amount of 0.1 to 35 weight %, preferred 0.5 to 25 weight % aptly.Peroxy bleaching compound can be used in combination with bleach-activating agent (bleaching precursor) to improve the bleaching action in low wash temperature.The bleaching precursor exists with the amount of 0.1 to 8 weight %, preferred 0.5 to 5 weight % aptly.
Preferred bleaching precursor is a peroxycarboxylic acid precursors, more particularly is peracetic acid precursors and mistake n-nonanoic acid precursor.The precursor of especially preferably bleaching that is suitable for using in the present invention is N, N, N ', N '-tetra acetyl ethylene diamine (TAED) and acyloxy Supragil GN in the ninth of the ten Heavenly Stems (SNOBS).In US 4751015 and US 4818426 (Lever Brothers Company) and EP 402971A (Uniliver) disclosed new quaternary ammonium and phosphorus bleaching precursor and in EP 284292A and EP 303520A (colored king) disclosed cationic bleaching precursor be interesting equally.
Bleach system can be augmented or replaces by peroxy acid.The instance of this peroxy acid can be found among US4686063 and the US 5397501 (Uniliver).Preferred examples is the peroxy acid of the acylimino peroxycarboxylic acid class described in EP A 325288, EPA 349940, DE 3823172 and EP 325289.Special preferred examples is that the NSC 308847 base is crossed oxy hexanoic acid (PAP).This peracid exists with 0.1-12%, preferred 0.5-10% aptly.
Can also there be bleaching stibilizer (polyvalent transition metal sequestrant).Suitable bleaching stibilizer comprises: edetate (EDTA), diethylentriamine pentacetate (DTPA), polyphosphonic acid salt; Such as Dequest (trade mark), ethylenediamine tetramethylene phosphoric acid salt (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP); And the nonphosphate stablizer, such as EDDS (ethylenediamine disuccinate).These bleaching stibilizers also can be used for particularly removing spot containing low-level bleaching species or do not contain in the product of bleaching species.
Preferred especially bleach system comprises peroxy bleaching compound (preferred randomly together with the SPC-D of bleach-activating agent), and as described in EP 458397A, EP 458398A and EP 509787A (Uniliver) and require the transition metal bleach catalyzer of protection.
Can also comprise one or more enzymes according to compsn of the present invention.Suitable enzyme comprises the and the following that can be used for being combined in the detergent composition: proteolytic enzyme, glycase, cellulase, oxydase, px and lipase.Preferred proteolytic enzymes (proteolytic enzyme) is in hydrolysis reaction, to make the spot degraded of the protein type that is present in the textile stains or the proteinaceous substances of the catalytic activity that changes.They can have any suitable origin, such as plant, animal, bacterium or yeast originates.
Have each mass and origin and in the various pH scopes of 4-12, have active proteolytic ferment or proteolytic enzyme be can get and can be used for the present invention.The instance of suitable proteolytic ferment is the subtilyne available from the special bacterial strain of Bacillus subtilus (B.Subtilis) and Bacillus licheniformis (B.licheniformis); Such as commercially available subtilisin Maxatase (trade mark), it is by the Gist Brocades N.V. supply of Delft ,Holland; With commercially available subtilopeptidase A lcalase (trade mark), it is by the Novo Industri A/S supply of Copenhagen, Denmark.
Particularly suitable is the proteolytic enzyme available from the bacterial strain of rod bacterium that in the pH of whole 8-12 scope, has maximum activity, and this proteolytic enzyme is commercially available, for example from registrar entitling Esperase (trade mark) and the Savinase (trade mark) of Novo Industri A/S.These are described among the GB 1243785 with the preparation of similar enzyme.Other commercially available proteolytic enzyme is Kazusase (can available from the trade mark of Japanese Showa-Denko), Optimase (from the trade mark of the Miles Kali-Chemie of West Germany Hanover), and Superase (can available from the trade mark of Pfizer).
Detergency enzymes is usually with the granulous form, use with about 0.1 to about 3.0 weight % amount.Yet, can use the enzyme of any suitable physical form.
In order to increase detersive power and to make handling ease, compsn of the present invention can contain alkaline carbonate, preferred yellow soda ash.Yellow soda ash can exist with the amount in 1 to 60 weight %, preferred 2 to 40 weight % scopes aptly.Yet, contain on a small quantity or not carbonated sodium compsn also within the scope of the invention.
Powder flowbility (powder flow) can for example lipid acid (or fatty acid soaps), sugar, propenoate or propenoate/maleate copolymer or water glass improve through adding a spot of pulvered structure material (structurant).A kind of preferred pulvered structure material is a fatty acid soaps, and the amount with 1 to 5 weight % exists aptly.The amount of water glass can be aptly in the scope of 0.1 to 5 weight %.
Other material that may reside in the detergent composition of the present invention comprises: water glass; Anti-deposition agent again is such as cellulose polymer compound; Soil release polymer; Inorganic salt are such as sodium sulfate; Suitable foaming control agent or suds booster; Proteolytic ferment and lipolytic enzyme; Dyestuff; Colored particle; Spices; Foam Control; The white dyes and the polymkeric substance (decoupling polymer) of uncoupling.This enumerate do not mean exhaustive.Yet according to a first aspect of the invention, many in these compositions will be better as the benefited agent in the material (benefit agent) group supply.
Preferred especially clothing with cleaning compsns in, said compsn comprises:
(a) the organic detersive surfactant that is selected from and the following of 5 to 60 weight %: anionic, non-anionic, cationic, amphoteric ion type and amphoterics and their combination,
(b) decontamination lotion promoter of 0 to 80 weight %,
(c) comb shape of 0.1 to 10 weight % or grafting branched copolymers and
(d) randomly, add to other decontamination composition of 100 weight %.
Wash washing composition for main, (in typical wash(ing)cycle process) typically produces 7 to 10.5 washing liq pH when cleansing composition is diluted in the washing liq.
The preparation of granular detergent composition
Granular detergent composition is aptly through the preparation of following method: the slurries spraying drying of composition that will compatible heat insensitive, spray then or the back feeds in raw material that those are inappropriate for the composition of processing through slurries.Skilled detergent formulation tDesigners will can not be difficult to determine which composition should be included in the slurries and which should not be included in the slurries.
Granular detergent composition of the present invention preferably has at least 400 grams per liters, the more preferably tap density of at least 500 grams per liters.Special preferred compositions has at least 650 grams per liters, the more preferably tap density of at least 700 grams per liters.
This powder can pass through back tower (post-tower) densification of spray-dried powders, or through there not being tower (wholly non-tower) method such as dry blending and granulation preparation fully; Under both of these case, can advantageously use high-speed mixer/granulator.Use the method for high-speed mixer/granulator for example to be disclosed among EP 340013A, EP 367339A, EP 390251A and the EP 420317A (Uniliver).
Liquid detergent composition can must prepare with optional ingredients through mixing it with any desired sequence, so that the compsn with the component that contains desired concn to be provided.According to liquid compsn of the present invention can also be conc forms, this means with the conventional liq washing composition to compare, and it contains the water of low levels.
To illustrate in greater detail the present invention through the following non-limiting example of reference now :-
Embodiment
In following examples, use following nomenclature to describe multipolymer :-
(monomer G) g(monomer J) j(branching agent L) l(chain-transfer agent) d
Wherein the value in the subscript is the mol ratio of each component, its by normalization method so that the monofunctional monomer value is 100, i.e. g+j=100.The degree of branching or branching level are represented with l, and d is meant the mol ratio of chain-transfer agent.
For example:
Methylacrylic acid 100Ethylene glycol dimethacrylate 15Dodecyl mercaptans 15Description contains methylacrylic acid with 100: 15: 15 mol ratio: ethylene glycol dimethacrylate: the polymkeric substance of dodecyl mercaptans.
Confirming of molecular weight: with THF (THF) or by the NaNO of 0.05M through under following condition, carrying out at the GPC that uses SEC-MALLs on the Wyatt chromatographic instrument 320% methanol aqueous solution that is adjusted to pH 9 is respectively as organic or water-based elutriant, and flow is that 1 ml/min and sample volume injected are 100 μ l.Apparatus preparation has the Polymer Laboratories PL mixed C and mixing D post group that is in 40 ℃.Use Wyatt Dawn DSP laser photometer and Jasco RI detector to detect.
Embodiment 1
Branching is gathered [methylacrylic acid-be total to-gather (terepthaloyl moietie) 22Monomethacrylates-altogether-ethylene glycol dimethacrylate]
MAA 95/(PEG 22MA) 5EGDMA 10DDT 10
With methylacrylic acid (MAA) (8.000g, 93mmol), gather (terepthaloyl moietie) 22Monomethacrylates (PEG 22MA) (4.651g, 4.7mmol), ethylene glycol dimethacrylate (EGDMA) (1.933g, 9.8mmol) and dodecyl mercaptans (DDT) (2.32cm 3, 9.8mmol) be dissolved in ethanol (126cm 3) in, and outgased in 30 minutes through purging nitrogen.After this time, reaction vessel is applied the forward nitrogen gas stream and 60 ℃ of heating.In case temperature equilibrium just adds AIBN (146mg is based on total monomer meter 1 weight %) with the beginning polyreaction, and keeps stirring 18 hours.Through the deposition of polymkeric substance in cold sherwood oil (petroleum) it is carried out purifying.The supernatant liquid decant is fallen and with cold petroleum ether polymkeric substance several times.With polymkeric substance in vacuum drying oven dry 48 hours, obtain the white solid of 80% yield.
Embodiment 2
Branching is gathered [diethyl aminoethyl methacrylate-be total to-gather (terepthaloyl moietie) 22Monomethacrylates-altogether-ethylene glycol dimethacrylate]
DEA 95/(PEG 22MA) 5EGDMA 10DDT 10
With diethyl aminoethyl methacrylate (DEA) (8.000g, 43mmol), PEG 22MA (2.162g, 2.2mmol), EGDMA (0.900g, 4.5mmol) and dodecyl mercaptans (1.08cm 3, 4.5mmol) be dissolved in ethanol (100cm 3) in, and outgased in 30 minutes through purging nitrogen.After this time, reaction vessel is applied the forward nitrogen gas stream and 60 ℃ of heating.In case temperature equilibrium just adds AIBN (110mg is based on total monomer meter 1 weight %) with the beginning polyreaction, and keeps stirring 18 hours.Through vacuum distilling ethanol is removed, and with the resulting clarification of perishing petroleum ether, oily polymer.With polymkeric substance in vacuum drying oven dry 48 hours to produce the sticky polymers of 85% yield.
GPC
Mn:4600; Mw:8100; Elutriant: THF
Embodiment 3
Branching is gathered [N-vinyl pyrrolidone-be total to-vinyl imidazole-be total to-gather by (terepthaloyl moietie) 22Monomethacrylates-altogether-ethylene glycol dimethacrylate]
VP 59/VI 31/(PEG 22MA) 10EGDMA 10DDT 10
With N-vinyl pyrrolidone (VP) (2.500g, 22.5mmol), vinyl imidazole (VI) (1.112g, 11.8mmol), PEG 22MA (3.817g, 3.8mmol), EGDMA (0.756g, 3.8mmol) and dodecyl mercaptans (0.912cm 3, 3.8mmol) be dissolved in ethanol (75cm 3) in, and outgased in 30 minutes through purging nitrogen.After this time, reaction vessel is applied the forward nitrogen gas stream, and 60 ℃ of heating.In case temperature equilibrium just adds AIBN (93mg is based on total monomer meter 1 weight %) and stirred 18 hours with beginning polyreaction and maintenance.Through vacuum distilling polymerization reaction mixture is concentrated, and resulting solution is precipitated in cold sherwood oil, use cold sherwood oil (coldether) washing then several times.With polymkeric substance in vacuum drying oven dry 48 hours to produce the light yellow solid of 90% yield.
Embodiment 4
Branching is gathered [monomethyl acryloxy propyl group end-blocking gathers (dimethyl siloxane)-altogether-Viscoat 335HP]
PDMSMA 100TEGDA 17DDT 17
With the end capped YSR 3286 of monomethyl acryloxy propyl group (PDMSMA) (1; 000Mwt, 6.75g, 6.75mmol), Viscoat 335HP (TEGDA) (0.225g; 1.125mmol), dodecyl mercaptans (0.223g, 1.125mmol) and AIBN (0.7g) be dissolved in anhydrous THF (50cm 3) in, and outgased in 30 minutes through making nitrogen pass the solution bubbling, then solution is sealed.Then solution was under agitation heated 18 hours to 70 ℃, allow its cooling then.Under reduced pressure remove solvent then, and with three (10cm of washing with acetone viscous soln 3), and last drying under reduced pressure is to produce clarifying viscous oil (5.2g).
Embodiment 5
Branched copolymers as effective deflocculant
Synthetic 6 kinds of multipolymers comprise a kind of line style and 5 kinds of branching, and estimate their stabilizations for kaolin (clay).Theory consists of:
DEA 95/ (PEG 22MA) 5(comparative example-linear copolymers)
DEA 95/ (PEG 22MA) 5EGDMA 2.5DDT 2.5(branched copolymers)
DEA 95/ (PEG 22MA) 5EGDMA 5DDT 5(branched copolymers)
DEA 95/ (PEG 22MA) 5EGDMA 7.5DDT 7.5(branched copolymers)
DEA 95/ (PEG 22MA) 5EGDMA 10DDT 10(branched copolymers)
DEA 95/ (PEG 22MA) 5EGDMA 15DDT 15(branched copolymers)
Wherein, as monofunctional monomer, PEGMA is for gathering (terepthaloyl moietie) methacrylic ester (Mn=1000gmol -1) and DEA be diethyl aminoethyl methacrylate.DDT is dodecyl mercaptans, i.e. chain-transfer agent.Numeral in the subscript is meant the relative mole composition of this component in polymer raw material.
4,20 ℃ of pH, in the ultimate density of 120ppm, test the stability of every kind of polymkeric substance for kaolin particle, said kaolin particle uses the particle of 2g/L.In all cases, confirm particulate stability, and compare with the stability of particle under the situation that does not have any polymkeric substance through the spectrodensitometry of locating at constant wavelength (450nm), as shown in table 1.Make that the stability of colloidal particles under the situation that does not have polymkeric substance is 100% nominal colloidal stability.In all cases, the existence of polymkeric substance increases colloidal stability.Yet, compare with simple linear polymer, the stability of colloidal solid is significantly higher for branched polymer.What is interesting is that as if the degree of branching have insignificant effect for colloidal stability.In fact, these branched polymers are more effective deflocculants.Yet highly branched polymer phase demonstrates insignificant improved stability for the analogue of slight branching.
Table 1. polymer architecture (degree of branching, promptly 1) is in the concentration of the 120ppm table data to the influence of the colloidal stability of kaolin particle (2g/L)
Polymer architecture (degree of branching) Do not have (contrast) Line style (l=0) l＝2.5 l＝5 l＝7.5 l＝10 l＝15
Normalized colloidal stability/% 100 184 342 363 389 383 376
Embodiment 6
Branching is gathered [dimethylaminoethyl methacrylate-be total to-gather (terepthaloyl moietie) 181-dimethacrylate]
DMAEMA 100(PEG 181DMA) 15TG 15
With dimethylaminoethyl methacrylate (DMAEMA) (1.000g, 64.6mmol), gather (terepthaloyl moietie) dimethacrylate (PEG 181DMA) (7.733g, 0.95mmol) and thioglycerin (TG) (0.083cm 3, 9.7mmol) be dissolved in THF (100cm 3) in, and outgased in 30 minutes through purging nitrogen.After this time, reaction vessel is applied the forward nitrogen gas stream, and heating under 70 ℃ of backflows.In case temperature equilibrium just adds AIBN (88mg is based on total monomer meter 1 weight %) with the beginning polyreaction, and keeps stirring 40 hours.Through vacuum distilling polymeric reaction solution is concentrated, and resulting clarification, viscous soln are deposited in the cold sherwood oil.With cold sherwood oil several times, then in vacuum drying oven dry 48 hours with this washing of precipitate.Obtain the polymkeric substance of the Off-white solid form of 90% yield.
GPC:Mn:29800; Mw:85900; Elutriant: THF
Embodiment 7
Branching is gathered and [is gathered (terepthaloyl moietie) 22Monomethacrylates-be total to-gather (dimethyl siloxane (5k)) dimethacrylate]
[PEG 22MA] 100[PDMS(5k)DMA] 15DDT 15
With the poly glycol monomethyl ether monomethacrylates (10.0g, 10.0mmol), the end capped YSR 3286 of methacryloxypropyl (PDMS (5k) MA; Mw 5000) (7.5g, 1.5mmol) and dodecyl mercaptans (DDT) (303mg 1.5mmol) is dissolved in toluene (75cm 3) in.Add AIBN (87mg, monomeric 0.5 weight %), and with solution with nitrogen-burst agitation 30 minutes to remove dissolved oxygen.Equip flask with condensing surface then, also use the nitrogen wash system and at the inert atmosphere lower seal.To react heating (at N 2Spent the night to 80 ℃ in 40 hours down).The cooling of permission flask, the required polymkeric substance (17.3g, 99%) of evaporating solvent afterwards to stay wax shape white solid form.(to 0.5mBar) removes residual solvent through pumped down on vacuum pipeline.This material water-soluble (translucent solution) and organic solvent such as chloroform and THF.
GPC:Mn:7300; Mw:11200; Elutriant: THF.

Claims (17)

1. soluble branched copolymers that can obtain through the addition polymerization method, said multipolymer is the reaction product of and the following:
(a) initiator,
(b) compatible chain-transfer agent (E and E '),
(c) the single unsaturated monomer (G and/or J) of at least a ethylenic, its each molecule contains a polymerizable double bond,
(d) the many unsaturated monomers of at least a ethylenic (L), its each molecule contains at least two polymerizable double bonds,
Wherein at least one in (a)-(d) has at least 1000 daltonian molecular weight, and (d) and mol ratio (c) greater than 0.0005: 1, wherein said branched polymer has following general formula
Figure FSB00000702158700011
Wherein
R and R ' represent Wasserstoffatoms or optional substituted alkyl independently of one another;
X and X ' represent to derive from the end group of termination reaction independently of one another;
The mol ratio of g, j and 1 each residue of expression, said mol ratio is made g+j=100 by normalization method, wherein g and j represent 0 to 100 independently of one another, and 1 is >=0.05; And
M and n are independently of one another＞1; And
Among E, E ', G, J and the L at least one has at least 1000 daltonian molecular weight, and the residue of wherein said chain-transfer agent accounts for 0.05 to 30 mole of % of said multipolymer.
2. multipolymer according to claim 1, wherein said multipolymer are comb shape or grafted branched copolymers, and among G and the J at least one have at least 1000 daltonian molecular weight, and
L has the molecular weight below 1000 dalton.
3. multipolymer according to claim 2 if wherein another among G and the J exists, then has the molecular weight below 1000 dalton.
4. multipolymer according to claim 1, wherein said molecular weight is hydrophilic monomers at least 1000 daltonian monofunctional monomers.
5. according to each described multipolymer among the claim 1-3, wherein said chain-transfer agent has the molecular weight below 1000 dalton.
6. multipolymer according to claim 1, wherein said multipolymer are the graft block copolymers of branching, and G, J and L have at least 1000 daltonian molecular weight.
7. multipolymer according to claim 6, wherein said chain-transfer agent have at least 1000 daltonian molecular weight.
8. multipolymer according to claim 1, wherein G and J represent to be selected from the ethylenic monofunctional monomer of and the following independently of one another: vinyl acid esters, vinyl aromatic (co) based compound, vinyl acid anhydrides, vinylamide, vinyl ether, vinyl amine, vinyl nitrile, vinyl ketone; The monomer of hydroxyl with can afterreaction to form the monomer of hydroxyl; The acid functional monomer; And zwitterionic monomer.
9. multipolymer according to claim 1, wherein 1 is 0.05 to 50.
10. multipolymer according to claim 1, wherein L is the polyfunctional monomer that is selected from and the following: many vinyl ester, many vinylamides, many vinyl aromatic (co)s based compound and many vinyl alkyl ethers.
11. multipolymer according to claim 1, wherein said chain-transfer agent is selected from: simple function mercaptan and multi-functional thiol and catalytic chain transfer agent.
12. multipolymer according to claim 1, wherein based on said monomeric gross weight, the residue of said initiator account for said multipolymer 0.01 to 3%w/w.
13. multipolymer according to claim 1, wherein said initiator is selected from: the molecule, redox initiator, superoxide and the iniferter that contain azo.
14. multipolymer according to claim 1, wherein said initiator is selected from persulphate.
15. one kind prepares the method for branched copolymers according to claim 1 through the addition polymerization method,
Said method comprises and the following is mixed together:
(a) at least a monofunctional monomer;
(b) mole number based on said monofunctional monomer is the polyfunctional monomer of at least 0.05 mole of %;
(c) chain-transfer agent; With
(d) initiator;
And make said mixture reaction subsequently to form branched copolymers.
16. a compsn, said compsn comprises branched copolymers according to claim 1 and carrier.
17. branched copolymers according to claim 1 is as the purposes of deflocculant.
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